Resinous polyhydric phenol



United States Patent 2,998,398 RESINOUS POLYHYDRIC PHENOL Sylvan OwenGreenlee, 3431Lhurel Drive,

West Lafayette, Ind. No Drawing. Filed Aug. 29, 19-58, Ser. No. 757,90220 Claims. (Cl. '26018) The invention relates to polyhydric phenols andmore particularly relates to polyhydric phenols which are miscible withcommercially available epoxides and, which contain sufficient reactivephenolic hydroxyls readily to form with epoxides, infusible, insolubleresinous products.

In the production of infusible, insoluble products by reaction ofpolyhydric phenols with epoxides it is essential that the two reactantsbe miscible one with the other in order to produce end products havingthe desired physical and chemical characteristics. Moreover, it isdesirable that curable mixtures of polyhydric phenols and epoxides. becharacterized. by stability when maintained for long periods of time atambient temperatures. However, the. polyhydric phenol-epoxide should.then readily be convertible tothe desired infusible, insoluble endproduct. by heating for a short period, of time, for example for a, halfan. hour, at temperatures in the neighborhood of 150 C.

Despite the great activity in the epoxy resin field in recent years, thepolyhydric phenols, employed forv reaction. with epoxides, to form,infusible, insoluble products. have not been entirely satisiactory.Difficulty has been. experienced in, obtaining the necessary miscibilitywith commercially available epoxides requisit to production of thedesired characteristics in the end, product. Additional difficulty hasbeen encountered in producing polyhydric phenols containing sufiieientactive phenolic hydroxyis per molecule to effect. the desired;reactivity in curing operations. Further, cured epoxy compositionsformed by reaction of, epoxides w th, c rr n ly availab e polyhydricphenols do not he. flfiXibility requisite to some. applications in whichother characteristics of the. epoxides are attractive.

One group of polyhydric. ph nols cu r ntly reac with polyepoxides, arethe phenol-formaldehyde condensates. The phenol formaldehyde condensateshave exhibited several rather seriousdeficiencies such as theliberation. of formaldehyde and water of condensation during the curingoperation. Moreover, the ,activity of '7 chain aliphatic structure.

ice

7 Z corporating in the polyhydn'c phenols suflicient long- For exampleU.S. Patent 2,665,266 describes a long-chain dihydric phenol prepared bycondensation of alkenyl phenol with phenol.

These products, however, are limited to two active phenolic hydroxylgroups per molecule, this number being insufficient to lend desiredreactivity either with commercially available aromatic or aliphatic typeepoxy resins. Accordingly desired film toughness is not obtained,particularly in compositions containing predominantly aliphaticstructures.

Another prior art expedient employed in an elfort to flexibilize thepolymerization products of polyepoxides with polyhydric phenols has beenthe incorporation into the composition of a plasticizer which does notstoichiometrically react with the epoxide compositions. Plasticizerswhich have been used for this purpose include dibutyl phthalate,sulfonamide plasticizers, polysulfide resins known commercially asThiokol resins, and polyamide resins. The latter two materials, inparticular, are known to react to some extent with the epoxidecompositions; however, their reactivity is not a definite stoichiometricreaction such that all ingredients are uniformly bound togethermolecularly. Another weakness of the commercial polysulfide andpolyarnide-type plasticizers is that of depreciating the good electricalproperties of epoxy resins, particularly at the higher temperatures. It

has been demonstrated, however, that the presence of ester and esterlinkages in these epoxy resin structures is not appreciably detrimentalto the electrical properties.

In using known plasticizing materials, the formulator is also limited tochoosing epoxide resins which are sufiiciently compatible with theplasticizers so that phase separation does not occur either duringapplication or during conversion of the mixture. In choosing theingredients based on miscilibity, therefore, the formulator is oftenconfronted with the choice of a combination v prepare resinouspolyhydric phenols of controlled, molecthe phenolic hydroxylj ofphenol-formaldehyde condensates is materially lower than that of thephenolic hydroxyl of phenols which have not been condensed withformaldehyde. The phenol-formaldehyde condensates are further deficientinthat it is almost impossible to control the number of phenolichydroxyl groups, present per molecule. Moreover, phenol-formaldehydecondensates exhibit the undesirable tendency to. condense withthemselves prior to reacting with polyepoxid'esto form the desired endproducts.

Other polyhydric phenols employed in reaction with polyepoxides havebeen the reaction products of dialdehydes with phenol such as thetetrahydric phenols described in U.S. Patent 2,806,016. Trihydrlcphenols have also been prepared by the reaction of phenol withunsaturated aldehydes such as acrolein as disclosed in U.S. Patent2,801,989. However these polyhydric phenols also are lacking in thedesired characteristics above described, viz., miscibility with epoxyresins, presence of the desired amount of reactive phenolic: hydroxyls,and flexibilizing action on, the cured. product,

Moreover, such polyhydric, phenols have also exhibited a tendency intheir purer form to crystallize, thus imparting non-homogeneity to theformulated, product.

' in the past, attempts have been made to introduce the desiredflexibility into cured epoxy compositions by inuia-r weight andfunctionality as expressed by the average number of phenolic hydroxylgroups per molecule.

It is a further object of this invention to prepare resinous polyhydricvphenols which, are miscible with commercial polyepoxides.

Another object of the invention is the preparation of resinouspolyhydric phenols characterized by reactivity with epoxides requisiteto production of insoluble, infusible products on heat treatment forrelatively short periods of time at elevated temperatures.

, An additional object of the invention is the preparation of resinouspolyhydric phenols; miscible with epoxides, the resulting mixture beingcharacterized by stability for long periods of time at ambienttemperatures but being readily converted to insoluble, infusibleproducts on heating for short periods of time at elevated temperatures.

Yet another object of the invention is a resinous polyhydric, phenol,miscible with commercial polyepoxides, possessing a sufficent number ofphenolic hydroxyl groups per molecule to react with commerciallyavailable polyepoxides and containing the desired aliphatic. structureto flexibilize the cured product.

It. hasnow been found that resinouspolyhydric phenols having at leastfour reactive phenolic hydroxyl groups prepared by the. reaction ofalcohol diphenols (hereinafter referred to as ADPs) with polybasic acidsor polybasic acid anhydrides under conditions which esterify thealcoholic content of the ADPs leaving the phenolic hydroxyl groupsessentially in the unreacted state may be reacted with pol'yepoxides(epoxides having an average in which X is the residue of a polyhydricphenol and A is the residue of an alcoholoc hydroxyl-containing moleculecontaining from 1 to 3 alcoholic hydroxyl groups. The polyhydric phenolspreferably are dihydric phenols or mixtures of dihydric phenols withamounts of higher polyhydric phenols below that causing substantial gelformation. For example, the invention contemplates mixtures of dihydricphenols with not more than about 25 mol percent of trihydric or not morethan about 12 15 mol percent of tetrahydric phenols or functionallyequivalent mixtures of the three. Preferably, penta-and hexahydricphenols will not be employed.

The ADPs employed for reaction with the polybasic acids or polybasicacid anhydrides in accordance with 2 the invention conveniently may beprepared by the reaction of polyhydric phenols with epihalohydrins,diepoxides or alcoholic hydroxyl-containing dihalohydrins using the polyhydric phenol in excess proportions such that there is present in thefinal composition unreacted phenolic hydroxyl groups after all of thehalide and/or expoxide groups have been reacted with phenolic hydroxylgroups. It is desirable that ADP composition contain not more 3alcoholic hydroxyl groups and preferably not more than 2 alcoholichydroxyl groups per molecule in order to give the desired degree ofcross-linking of the ADP molecules in reaction with polybasic acids.Preparation of specific preferred ADPs is illustrated by the followingschematic formulae:

1) Reaction of 3 mols of bis(4-hydroxyphenyl)dimethyl methane knowncommercially as bisphenol A with 2 mols of epichlorohydrin C CH;

HO O r as" or" (2) The reaction of 2 mols of tetrachlorobisphenol A with1 mol of 1,3-glycerol dichlorohydrin (3) The reaction of 2 mols of themethyl ester of 4,4'-bis(4-hydroxyphenyl)pentanoic acid with 1 mol ofdiepoxybutane HO OH O O mam Haas H3 7 CHIOHZCOZCHa no O-CHaCHOHCHOHCHgOon 7 5 K n CHzCHzC 0,0113 on, anionic 020113 It is understood that thesereactions as illustrated by Formulae 1, 2, and 3 do not give purecompounds but give mixed products in which the predominating structureis that shown by the formula and the average composition approaches thatshown by the formula. Illustrative of the available polyhydric phenolswhich may be used in i this preparation are bisphenol A, halogenatedbisphenol o-orncnoncmo A, hydroquinone, resorciuol,bis(4-hydroxyphenyl)sulfone, a bisphenol prepared from the condensationof 1 mol of dipentene with 2 mols of phenol (US. Patent 2,811,564.),alkylidene diphenols prepared from methyl ketones and cyclic ketoneswith phenol, dihydroxy naphthalenes, phloroglucinol, and trihydricphenols prepared by the condensation of acrolein with phenol (US. Patent2,801,989).

US. Patents 2,510,885; 2,510,886; and 2,592,560 disclose the preparationof ADPs by the reaction of excess portions of dihydric phenols withdihalides, epihalides, and-.diepoxides. The conditions for the reactionof an aliphatic hydroxyl-containing dichloride with excess quantities ofa polyhydric phenol are essentially those of heating the mixture in thepresence of sufiicient alkali to neutralize the chloride content.Likewise, the reaction of epihalohydrins with excess portions ofpolyhydric phenols in preparing the ADPs consists of heating thereaction mixture in the presence of sufiicient alkali to neutralizethechloride content of the epihalohydrin. The reaction ofa' diepoxide withexcess quantities of polyhydric-phenols is normally carried out byheating the mixturefat, temperatures of from 200 C. in the presence ofsmall quantities of alkaline catalysts such as potassium hydroxide,sodium hydroxide, or tertiary amines.

Illustrative of the dihalo alcohols, epihalohydrins, and diepoxideswhich may be used in reaction with the dihydric and trihydric phenols toprepare alcoholic phenols are glycerol dichlorohydrin, epichlorohydrin,diepoxy 2 no on c1 c1 or Cl +c1oHroHonomo1+2Naon c as butane, limonenediepoxide, digl-ycidyl ethers, ofi dihydric fication of corn oil,cottonseed. oil, soybean oil, linseed.

phenols, and. Polyglycijdyl ethers, of; glycerol and. neuter oil, andChina wood oil. Some of the unsaturated acids, erythritol. 1constituting marine oils, contain more than l8-carbon Polybasic: acidswhich: may be usedin reaction with the; chains. These unsaturated acids,too, may be used in prealcoholic hydrQXyl conten of the. ADBsrincludesuch, paring the dimer and trimeraacids. Another source of acids as theisomeric phthalic, malonic, methyl malonic the polymerized vegetableandmarine oil type aliphatic succinic, methyl succinic, sym-dimethylsuccinic, unsym acids is; that of, the so calledl oil pitches. Thesematerials, dimethyl succinic, glutaric, adipic, pimelic, suberic,azelawhich arev often the residues of the long-chain acid distilic,sebacic, brassilic, maleic, fiumaric, citraconic,. mesa- 'lati'onprocess, are essentially crude, highly polymerized conic, itaconic,glutaconic, tricarballylic, aconiti'c, and 10 acids. These materialsarev valuable in esterification of citric acids;endo-cis-ibicyclo(2,2,1)-5-heptene 2,3-dithe alcoholic diphenols inpreparing the flexibilizing, carboxylic anhydride, dimerized rosin, the,OXyacetic acids resinous, polyhydric phenols of this invention. preparedfrom polyhydric phenols, and saturated and un- Another source oflong-chain aliphatic dibasic acids saturated long-chain aliphatic acidssuch as. hexadecanehaving at least 16' carbon atoms per molecule are thedioic,heptadecanedioic, octadecanedioic, nonadecanedioic, acidsprepared, for example, by the reaction of cyolo eicosanedioic,heneicosanedioic, docosanedioic, tricohexanone with hydrogen peroxideand butadiene in a0- sanedioic, tetracosanedioic, pentacosanedioic,hexacocordance with U.S. Pat ,4 and ,7 sanedioic, heptacosanedioic,octacosanedioic, nonacosane- Typical, of these acids is 8,12-eicosadienedioic acid havdioic, triacontanedioic, hentriacontanedioic,dotriaconing the formula tanedioic, tetratriacontanedioicpentatriacontanedioic, 20 HO C CH CH cHzcHcH CH CH:hexatriacontanedioic, octatriacohtanedioic, hexatetracon- 2 2 2tanedioic, 8,12-eicosadienedioic acids, and dimers and CHCH2(CH2)5CO2Htrimers of acids such as 9-hexadecenoic, 9-octadecenoic, Thesedlenedlolc acldsi g the genaral formula 9,12-octadecadienoic, 9,12,15octadecatrienoic, 9,11,13- [CHZCH=CHCH2(CHZ)MO 5C02H12 octadecatrlenoic,6-octadeceno1c, ll-octadecenoic, 9-e1c0- senoic, ll-docosenoic,l3-docosenoic, IS-tetracosenoic, hydrtgenated glve h i f f 17 hzun'acontenoic, 6,10,14pheXadecatrL dloic aclds WhlCh are also valuabledibasic ac ds for ester enoic, l0,12 l4-octadecatrienoic,4,8,12,l5+octadecatetra- 'f f of alcohohc dlPhenols i f flexl enoic,9;1'1,13-,IS-OctadecatetraenOic, and 5,8,11,14-eicosablhzmgz resmousPolYhYdncof thls mvfmtlon tetraenoic acids. A typical structure of aflexibrlizing polyhydric phenol Many of the commercial polybasic acidssuch as y be Shown y the following l' l based on phthalic, maleic, andsuecinic acids, are available comfication of 2 m ls of an alcoholicdiphenol from b1 mercially in the anhydride form, and these anhydridesphenol and epichlorohydrin with 1 mol of di-oleic acid are convenientlyused in reaction with the ADPs to (9-octadecenoic acid).

a Cw 0 0 CH;

O r l cm 0 v bum rim.

C ta. (5Q CH. Ca @011 0 give the cross-linked esters of this invention.There are Esterification of the ADPs, with polybasic acids or alsoavailable a number of anhydrides prepared by the polybasic acidanhydrides is conveniently carried out by Diel's-Ald'er reaction ofmaleic. anhydride with dienes heating the reactants at hightemperatures, usually in: the suchas butadiene, cyclopentadiene,methylcycl'opentatemperature range of 190300 C. until the desired aciddiene,and piperylene, and these anhydrides are valuable value isobtained. The high temperature esterification coupling agents foresterification of the ADPs to give may be carried out inv the presenceof aninert gas passed the resinous polyhydric phenols of this invention.Therethrough the continuously agitated mixture so. as to remove fore,when the word acid is employed in the appended the water of condensationas it is formed. Another pro,- claims it is intended to embrace both theacid and its cedure of high temperature esterifieation commonly usedanhydride where such anhydrides exist. is that of adding suflicienthydrocarbon solvent to give In accordance with the inventionit has beendiscovered constant reflux at the esterificationtemperature permittingthat when the acid reacted with ADP is along-chain the reflux solvent toreturn to, the reaction mixture-from aliphatic acid in which the'acidstructure contains an alia reflux condenser attached to the reactionchamber phatic chain having atleast sixteen carbon atoms, the rethrougha water leg which serves to prevent the water of sulting resinouspolyhydric phenol exerts a marked flexicondensation firorn returning tothe: reaction mixture. bilizing effect on the cured product of thepolyhydric Another method which might be used in preparing the phenoland polyepoxide. subject resinous polyhydric phenols is that of thealco- The aliphatic, polybasic, acids which maybe employed holysis oflow molecular weight alcohol; esters. of the include, the, polymerizedvegetable oil acids. Commerpolybasic acids with the ADPs; To illustrate,the ADP cijally available polymerized vegetable oil acids are illusmightbe heated with the dimethyl ester of isophthalic trated bythe;so-called; dimer and trimer acids. containing acid at 200-235 C. in thepresence of a trace of calcium 2. and 3 carbonylie acid: groupspermolecule and obtained acetate, thus giving liberation of methanol andesterificaby polyrncnining lit-carbon; aliphatic olefin-containing tion.of the alcoholic content of the ADP.v vegetable oil acids. Typical acidsused in preparing these In accordance. with the invention, the resinous,polydimer andtrimcr acids are the acids, prepared. by sapom'r '(5 hydricphenols have at least tour phenolic, hydroxyls per molecule and arecharacterized by the structural formula:

wherein A is an alcoholic hydroxyl containing residue, X is the residueof a polyhydric phenol and R is the residue of a polycarboxylic acidconnected to A by an ester linkage. The polycarboxylic residue R maycontain additional carboxyl groups.

The following examples will serve to illustrate the preparation ofresinous polyhydn'c phenols described herein. Softening points as usedherein were run by the Durrans mercury method (Journal of Oil & ColourChemists Association, 12, 173-175 [1929]). Acid values are defined asthe number of milligrams of potassium hydroxide equivalent to the freeacid contained in a onegram sample. Epoxide contents are measured byheating one-gram samples with an excess of pyridine containing pyridinehydrochloride (made by adding 16 cc. of concentrated hydrochloric acidper liter of pyridine) at the boiling point for 20 minutes and then backtitrating the excess pyridine hydrochloride with 0.1 N potassiumhydroxide using phenolphthalein as indicator and considering that 1 molof the HCl is equivalent to 1 epoxide group. Proportions expressed areparts by weight unless otherwise indicated.

Examples I through VI illustrate the preparation of alcoholic diphenolsused in reaction with the polybasic acids and polybasic anhydrides togive the resinous polyhydric phenols of this invention.

EXAMPLE I Preparation of an alcoholic diphenol from 2 mols of bisphenolA (BPA) and 1 mol of epichlorohydrin (Epi) Ingredients:

BPA 1,824 parts (8 mols). NaOH (97.9%) 327 parts (8 mols).Epichlorohydrin 370 parts (4 mols). H O 1,824 parts. H S (6N) 798 parts.

The reaction was carried out in an 8-liter stainless steel beakerprovided with a mechanical agitator, thermometer, and a bafile blade(large spatula). The BPA and NaOH were dissolved in the water byheating, with agitation, to 70-75" C. The mixture was cooled to 50 C.and all of the Epi added after which the temperature rose to 75-80 C.through exothermic heat. The temperature was raised to 90-95 C. over aperiod of 15 minutes and held at this temperature for 1 hour continuingagitation throughout the reaction period. The sulfuric acid was addeduntil the solution was acid to litmus while holding the temperature at80-95 C. with continuous stirring. The water-salt layer was removed bydecantation and the tafiy-like resin washed 45 times by stirring, eachtime with about 2 liters of water at 90 C. for a period of 15-20minutes. After decantation of the last wash water, the resin was driedby stirring and heating to a final temperature of 150 C. givingapproximately 2000 parts of a straw-colored resin melting at 77.5" C.Analysis showed this resin to contain a total of alcoholic and phenolichydroxyl content of 10.3% by weight, no epoxide content, and an acidvalue of 3.

EXAMPLE II Preparation of alcoholic diphenol from 3 mols of bisphenol Aand 2 mols of epichlorohydrin Ingredients:

BPA 1,824 parts (8 mols). NaOH (97.9%) 327 parts (8 mols).Epichlorohydrin 493 parts mols). H O 1,824 parts.

H2SO4(6N).. 534 parts.

8 The preparation was made in accordance with the procedure described inExample I. The straw-colored, resin, ous product amounting to 2,099parts had a softening point of 89 C., a total alcoholic and phenolichydroxyl content of 9.5% by weight, no epoxide content, and an acidvalue of 2.5.

EXAMPLE III Preparation of an alcoholic diphenol from 2 mols of tetrachlorobisphenol A and 1 mol of epichlorohydrin Ingredients:

Tetrachlorobisphenol A 732 parts (2 mols). NaOH (97.9%) 82 parts (2mols). Epichlorohydrin 92.5 parts (1 mol). H O 736 parts. parts.

The preparation was made in accordance with the procedure described inExample I giving a resinous product having a softening point of 64 C.,an acid value of 186, a total hydroxyl content of 7.2%, and no epoxidecontent. The acid value represents partial titration of the phenolichydroxyl content using phenolphthalein as an indicator and titratingagainst methanolic potassium hydroxide.

EXAMPLE IV Preparation of an alcoholic diphenol from 2 mols of resrcinol and 1 mol of limonene diepoxide Ingredients:

Resorcinol '110 parts (1 mol). Limonene diepoxide 84 parts (1equivalent). DMP- 30 [tris(dimethylaminomethyl) phenol, available fromthe Rohm & Haas Company] 3.88 parts.

The resorcinol, limonene diepoxide, and DMP-30 were heated together in astainless steel beaker until molten and then heated with continuousagitation to C. and held at this temperature for 1 hour. The resinousproduct had a softening point of 72 C., an acid value of 120, a totalhydroxyl content of 16.3%, and an epoxide content of 0.

EXAMPLE V Preparation of an alcoholic diphenol from 2 mols of dipentenediphenol (condensation product of 2 mols of phenol with dipentene inaccordance with Patent No. 2,811,564) and 2 equivalents of Epon 562(dehydrohalogenated reaction product of glycerol with epichlor hydrinhaving an equivalent weight to epoxide of approximately 150-marketed byShell Chemical Corp.)

Ingredients:

Dipentene diphenol 324 parts (1 mol). Epon 562 150 parts (1 equivalent).DMP-30 [2,4,6 tris(diethylaminornethyl) phenol, marketed by Rohm & HaasCompany] [4.74 pants.

To a molten mixture of the dipentene diphenol and Epon 562 in astainless steel beaker provided with a thermometer and a mechanicalagitator was added slowly with rapid agitation the DMP-30. The reactionmixture was heated with continuous agitation at l72-l95 C. over a periodof 35 minutes and held at -199 C. for a period of 1 hour. The resinousproduct had a softening point of 102 C., an acid value of 6.4, a totalhydroxyl content of 6.85%, and an epoxide content of 0.

EXAMPLE Preparation of an alcoholic diphenol from 2 mols of CardoliteNC-512 and. a digylcidyl. ether of bisphenol A The digylcidylether of.bisphenol A had an epoxide equivalent weight of 1 75. CardoliteNC-512 isa commercial. dihydric. phenol obtained, from the Minnesota Mining andManufacturing Company and. stated to have the. following structurev (cH27- J mm Ingredients:

NC-512 274 parts (.5 mol). Dlglycidyl ether of EPA. 58 parts (.25equivalent). DMP30 v 3.32 parts.

To a molten mixture of NC-512 and the diglycidyl ether of EPA in a.stainless steel beaker provided with a thermometer and a mechanicalagitator was added slowly with agitation the DMP-30. The reactionmixture was heated with continuous agitation at 175-196 C. for 20minutes and held at 196-200 C. for 1 hour. The resinous product had asoftening pointof 55 C., an. acid value of 6.6, a total hydroxyl contentof 5.9%, and. an epoxide content of 0.

Examples VII through XXI. illustrate preparation of the resinouspolyhydric phenols by esteriiication of the alcoholic diphenols withpolybasic acids and polyhasic acid anhydrides.

EXAMPLE V11 Esterification of the ADP of Example I with phthalicanhydride A mixture of 512 parts of the resin of Example I and 59.24parts (.8 equivalent to the alcoholic hydroxyl content), of phthalicanhydride was placed in a 1-liter, 3-neok flask; provided with athermometer, a, mechanical agitator, and: a condenser attached through awater leg. The mixture. was heated and agitation initiated as soon asthe mixture had become molten. When the temperature had reached 19(1 C.50 parts of xylene was added and heating continued with continuousagitation to 250 C. At this point the amount of xylene. present inthemixture was regulated to give constant reflux into the condenser so. asto remove the water of condensation into the water leg as, the reactionproceeded. The reaction mixture. was heated at 250 to 267 C. foraperiod. of 4 hours; and 2.0 minutes at which time the pressure wasreduced. to .135, in order to remove the. xylene from the, resinousproduct, The product had a softening point of 9,1.5 C. and. l acid valueof 3.

EXAMPLE VIII Esterification of the; ADP of Example IV with saccinic acidA mixture of 77.6 parts of the resinous dihydric phenol of Example IVand 12.8 parts of succinic acid was heated together in a stainless steelbeaker. When the mixture had reached the molten state,mechanicalagitation was initiated and continued throughout the reactionperiod. The reaction mixture was heated in the temperature range of 232to 243 C. for 2' hours and 32 minutes to. give a: product having asoftening point of 160 C. and an acid value of 110. 1

EXAMPLE, I-X

Esterification' of the ADP of Example III with maleic anhydride A.nnKture: of; 396- parts of the, ADP of Example. III and 31 parts ofmaleic anhydride wereesterified in accordance with the method describedin Example VII using xylene as the reflux solvent, and heating thereaction mixture at 230 to 245 C. for a period of 3 hours and 43 minutesto give a product having a softening point of 130 C. andanacid value of180.

EXAMPLE. X

Esterification of the ADP of Example V1 with endo-cisbicyclo('2,2,1)-5.-heptene-2,3dicarboxylic anhydride A mixture of- 117 parts ofthe resinous ADP of Example VI and' 8.2 parts of endo-cis-bicyclo(2,2,1)-5- EXAMPLE XI Esterification of the resinous ADP of Example Iwith adipic acid,

In accordance with the method described in Example VII, a mixture oh384; parts of the resinous ADP of Example I and 73. parts oi adipic acidwas ester-iiied inthe presenceof refluxingxylene-for a period of 3 hoursand 13 minutes at 240-26l C. followed by removal of the xylene to give aproduct having a softening point of 95.5 C. and an, acid value of 10.5.

EXAMPLE XII Esterification of the resinous ADP of Example I with azelaicacid In. accordance with the procedure described in Example VII, amixture of 1024. parts of the resinous ADP of Example I and 14.1 partsof azelaic acid washeated in the presence of refluxing xylene in thetemperature range of 255 to 278 C. for a period of 5 hours followed byremovalof the xylene to give a resinous product having asoftenlng pointof C. and an acid value of 6.1-.

EXAMPLE XII-I Esterification of the resinous ADP of Example I withdimerized rosin (Dimerex resin obtained from the Hercules Powder,Company) A mixture of 480 parts of the dimerized rosin: and 1024' partsof the resinous ADP of Example I was cs,- terified in the presence ofrefluxing xylene. at 270 to 280 C. for a period of 5. hours and 5.0.minutes followed by removal of the xylene to give a product having asoftening point of 94 C; and an acid value of 10.

EXAMPLE XIV Esterification of the resinous. ADP of Example I] withdimerized rosin In accordance with the procedure described in ExampleVII except replacing the refluxing xylene with a constant bubbling ofcarbon. dioxide through the reaction mixture, a mixture of 398, parts ofthe resinous ADP of Example II and 265 parts of dimerized rosin washeated at 255 to 271 C. fora period of; 6 hours to give a product havinga softeningpointofi; 1.01 C- end n'acid, v lue of 4.4.

11 EXAMPLE XV Esterification of the resinous ADP of Example I with aC-36 dimerized vegetable oil acid (dimer acid 3079-S, acid value 190,dimer acid content 95%, trimer acid content 4%, monomer acid content 1%,obtained from Emery Industries, Inc.)

. A mixture of 400 parts of the resinous ADP of Example I and 174 partsof the dimer acid was placed in a 2-liter, B-neck flask provided with athermometer, a mechanical agitator, and a condenser attached through awater leg. The mixture was heated and agitation initiated as soon as themixture had become molten. When the temperature had reached 190 C., 100parts of xylene was added and heating continued with agitation to 240 C.The amount of xylene present in the mixture was regulated so thatconstant reflux into the condenser was attained so as to remove thewater of condensation into the water leg as the reaction proceeded. Thereaction mixture was heated for 1 hour at 240-245 C. and the temperaturethen increased to 270 C. and held in the range of 262-275 C. for aperiod of 5 hours and 40 minutes. The acid value on the nonvolatilecontent at this point was 5.8 and the softening point was 74.5 C. Thexylene was removed from the product by reducing the pressure to 15 mm.of mercury, keeping the pot temperature at 250 C. while rapidlyagitating the reaction mixture.

EXAMPLE XVI Esterification of the resinous ADP of Example I] with dimeracid 307 9-S EXAMPLE XVII Esterification of the resinous ADP of ExampleI with C-54 trimerized vegetable oil acids (Emery trimer acid No.3055-8, acid value 190, trimer acid content 70-85%, dimeracid content15-3'0 (available from l Emery Industries) A mixture of 256 parts of theresinous ADP of Ex- -ample I and 225 parts of the trimer acid was heatedin a stainless steel beaker provided with a mechanical agitator, athermometer, and a means of bubbling CO into the reaction mixture. Withcontinuous addition of car- -'bon dioxide the reaction mixture washeated to 140 C.

at which point mechanical agitation was initiated. The mixture washeated gradually to 228 C. and held in the range of 228-232 C. tor ajeriod of 1 hour and 20 minutes.

The reaction product had an acid value of 50 and a softening point of675 C.

EXAMPLE XVIII Esterification of the resinous ADP of Example I withcotton seed pitch, a polymerized residual acid from hightemperaturedistillation of cottonseed oil acids having an acid value of 85(available from Armour Chemical Division of Armour and Company) Inaccordance with the procedure described in Example XV, a mixture of 256parts of the resinous ADP of Example I and 300 parts of the cottonseedpitch was esteritied with continuous agitation in the presence ofrefluxing xylene. The temperature was gradually raised to 268 C. andheld at 268-275 C. for a period of 1 hour and '20 minutes. The reactionmixture was allowed to cool to 200 C. and further cooled by addingsuflicient xylene to give a nonvolatile content of' 67%. on thenonvolatile content was 12.

EXAMPLE XIX Esterification of the resinous ADP of Example 111 with C-54trimer acid 3055-S The acid value EXAMPLE XX Esterification of theresinous ADP of Example V with dimer acid 3079-5 A mixture of 47 partsof the resinous ADP of Example V and 11.5 parts of dimer acid (Emery No.30794) was heated with continuous agitation in a stainless steel beakerfor a period of 1 hour gradually raising the temperature from to 210 C.The product at this point had an acid value of 23. It was dissolved inxylene to give a nonvolatile content of 50%.

EXAMPLE XXI Esterification of the resinous ADP of Example VI with thedimethyl ester of a C-20 dibasic acid, eicosadienedioic acid (availablefrom the Shell Chemical Corporation) In a l-liter, 3-neck flask providedwith a thermometer, a mechanical agitator, and a condenser attached to avacuum system was placed 117 parts of the resinous ADP of Example VI and37 parts of a dimethyl ester of the 0-20 dibasic acid, eicosadienedioicacid, and .2 part of sodium methoxide. The reaction mixture was heatedto 227 C. and held in the range of 227235 C. for a period of 2 hours and45 minutes keeping the reacting system at a pressure of 15 to 20 mm. ofmercury throughout the reaction period. The resulting product was asemi-solid, resinous material having complete solubility in xylene.Xylene was added to give a product containing 50% nonvolatile content.

Products of the type described in Examples VII to XXI representing theresinous polyhydric phenols of this invention need not be of high purityto be of value in reaction with polyepoxides to produce infusible,insoluble commercial products. In general, it has been found that whenthe alcoholic diphenols such as those described in number of phenolichydroxyl groups per molecule to .readily convert polyepoxides to theinsoluble, infusible products. In the case where less than oneequivalent amount of polybasic acid of polybasic acid anhydride is usedin esterification of one mol of the ADP, the product would consist of amixture of some unreacted ADP and some coupled ADP of higherfunctionality. In the case where more than equivalent amounts of thepolybasic acids or the polybasic acid anhydrides to the alcoholichydroxyl content of the ADP are used in esterification there would bepresent in the composition some free carboxylic acid groups as Well asthe phenolic hydroxyl groups. Such mixed compositions from using excessquantities or deficient quantities of the acid or anhydrides foresterification give excellent reactivity when used in combination withthe polyepoxides to form the insoluble, infusible products. The newresinous polyhydric phenols containing in the over-all composition anaverage of at least 4 phenolic hydroxyl groups per molecule giveexcellent conversion of epoxides such as the accuses bydehydrohalogena-tion as illustrated by the commercial" resin, Epon 562,to give valuable infusible, insoluble products. It has been observedthat mixtures of the new resinous polyhydricv phenols with po-lyepoxidesin thepresence of catalysts such as alkali'phenoxides or tertiary aminesare stable for long periods of time at room temperature whether they bestored as solvent solutions or in the. solid state. This is ofparticular. value in that such mixtures may be stored in solutions forseveral weeks before application as coating or impregnating materials,they may be stored for long periods of time as thin films which. havebeen deposited from the solvent solutions, or they may be stored forlong periods of time in thick lay-. ers corresponding to molded objectsfinally completing conversion after the long period of standing by theapplication of heat such that the material is heated, for example, inthe temperature range of- 75 to 200 C. for periods rangiugfrom less than1 minute up to. 1 or 2 hours depending on the particular composition,the catalyst, the amount of. catalyst, and the temperature of baking.Examples XXII through XXXVII demonstrate the. utility of the newresinous polyhydric phenols. in reactions with polyepoxides top repareinfusible, insoluble materials suitable for use as coatings, adhesives,and. molding resins.

EXAMPLE XXII A mixture of 113 parts of the resinous polyhydric phenol ofExampl' VII, 133 parts of polyallyl' glycidyl ether (PAGE), and .84 partof DMP-30 dissolved in methyl isobutyl ketone to give 50% nonvolatilesremained sufiiciently fluid for application as a varnish for a period of2' months. Thin films .003-inch thickness prepared from this varnishcured to an extremely hard, yet flexible, material on baking. for 10minutes at 150 C. This film showed no signs of deterioration onsubjecting to boiling water for a period of 24 hours or on subjecting to5% aqueous sodium hydroxide heated at 90" C. for a period of 1 hour.

A similar hard, tough, infusible film was obtained on baking for 30minutes at 150 C., a .003-inch thick wet fihn from a solution of 38parts of the resinous polyhydric phenol from Example VII, 55 pants of acommercial epoxy resin having a softening point of 70 C. and an epoxideequivalent weight of 500- (Epon- 100] based an bisphenol A andepichlorohydrin and obtained from the Shell Chemical Corporation), and 1part DMP-30 dissolved in methyl isobutyl ketone to give 50% nonvolatilecontent. The latter film, too, showed outstanding resistance to boilingwater and aqueous alkali;

EXAMPLE XXIII A mixture of 388 parts of the resinous polyhydric phenolcomposition of Example VIII and 400* partsof a commercial diglycidylether of bisphenol A having an epoxide equivalent weight of 195 (Epon828 available from the Shell Chemical Corporation) and 8 parts of DMP-30dissolved in methyl isobutyl ketone to give 50% nonvolatile content gavea varnish which when spread in .003-inch wet film thickness convertedinto an infusible, insoluble material on heating for 15 minutm at 150 C.This film was unafiected by submitting to boiling water for a period of24 hours.

EXAMPLE XXIV A 50% methyl isobutyl ketone solution of a mixture of 421parts of the resinous polyhydric phenol of Example TX, 133' parts ofPAGE, and 4.5 parts of DMP-30 applied as a .003-inch wet filmandbakedior 15 minutes at;

125 Clgave anextremely hard, infusiblematerial. film showed no. signs ofdeterioration on subjecting it to boiling water for a period of 5.5hours or to 5% aqueoussodium hydroxide at. C. for a period of 2 hours.

EXAMPLE. XXV

A510.% xylene solution of a mixture of 800' partsof the resinouspolyhydric phenol of Example X, 500; parts of Epon 828, and 11- parts ofDMP-30 gave a varnishwhich. whenv spread in .003-inch wet films andbaked for 30; minutes at 150 C. gave a hard, flexible, infusible productWhlChgWlthSlOOdbOlllDg water for 24 hours and 5%: aqueous: NaOH at roomtemperature for 10 hours without signs of deterioration;

EXAMPLE XXVI EXAMPLE XXVII Av 37 methyl isobutyl ketone solution of amixture of 40.5 parts of the resinous polyhydric phenol of Example XII,28 parts of Epon 828, and 0.7 part of DMP- 30 gave a varnish, thin filmsof .OOS-inch wet film thickness of which, gave extremely hard, infusibleproducts on baking for 10 minutes at 150 C. Such films weresubjected toboiling water for a period of 48 hours and also to 5% aqueous sodiumhydroxide at 90 C. for 5 hours with no visible indication ofdeterioration. The 37% solution'had an original viscosity of 3.7 poisesand a viscosity of 22.7 poises after 1 week.

A .003-inch wet film of this same composition was. permitted to. standat room temperature for a period of 1. month as a tack-free film afterhaving lost the solvent in a matter of a few. hours and then wassubjected to heating at C. at which. time the film fused to tackinessfollowed. by conversion to the infusible, non-tacky state amatter oct 30minutes.

EXAMPLE XXVII I- A mixture of 50. parts of the resinous polyhydricphenol of Example XII and 31 parts of Epon 828 were fused together andstirred. rapidly while 1.6 parts of DMP-30' was added to the mixturebeingstirred rapidly at 100 C. for about 30. seconds and poured into athin layer so as to obtain rapid cooling. This material was broken upinto small particles and samples of about 10 grams were baked in a l/z-inch diameter aluminum dish at various periods after standing for2'months. Material which had stood at room temperature fora period of 2months fused together and converted to a flexible, infusible, insolubleobject on heating for 30 minutes at C.

EXAMPLE XXIX A mixture of 370 parts of the resinous polyhydric phenol ofExample XIII, 133 parts of polyallyl glycidyl ether, and 5 parts ofDMP-30 in methyl isobutyl ketone to give a nonvolatile content of 65%was spread in .003- inch Wet films and baked- 1 hour at 150 C. to give aflexible, infusible film. This film withstood boiling water for 10 hourswithout showing any signs of deterioration.

EXAMPLE XXX A mixture of 300 parts of the resinous polyhydric phenol ofExample XIV, 133 parts of polyallyl glycidyl ether, and 4.3"parts ofDMP-30 dissolved in methyl iso- 15 butyl ketone to a nonvolatile contentof 65% was spread in .003-inch wet films and baked 30 minutes at 150 C.to give a flexible, infusible film. This film showed no signs ofdeterioration on exposure to boiling water for 10 hours.

EXAMPLE XXXI A mixture of 50 parts of Epon 1001 (a polyepoxide preparedfrom bisphenol A and epichlorohydrin having an epoxide equivalent weightof 500 and available from Shell Chemical Corporation), 36.2 parts of thedimer acid ester of Example XV, and 0.86 parts of DMP-30 was dissolvedin an equal weight of methyl isobutyl ketone. A film of this varnishhaving a wet film thickness of 0.003-inch became tack free on heatingfor minutes at 150 C. The same film baked for 30 minutes at 150 C.remained flexible and showed no signs of deterioration on exxposure toboiling water for 48 hours, to 5% aqueous NaOH at room temperature for24 hours, and to 5% aqueous NaOH at 90 C. for 5 hours.

The resistance of this product to 5% aqueous NaOH at 90 C. is verysurprising as the composition does contain ester groups. The extremeisolubility is apparently of such magnitude that the hot causticsolution cannot chemically contact the ester groups.

A similar composition without the solvent showed good cure to aninfusible object on heating in thick layers (0.5 inch) for 30 minutes at150 C. This same composition of the dimer ester, Epon 1001, and DMP30stored at room temperature for a period of 30 days and then subjected toheating at 150 C. fused and then converted to an infusible object.

EXAMPLE XXXII A mixture of 69 parts of the dimer ester of Example XVI,26 parts of polyallyl glycidyl ether (epoxide equivalent weight=l33 andcontaining an average of 3.5 epoxide groups per molecule) and 0.96 partDMP-30 was dissolved in methyl isobutyl ketone to give 67% nonvolatilecontent. This varnish had an initial viscosity of 3.1 poises and aviscosity at the end of 2 weeks of 31.6 poises. Films of 0.003-inch wetfilm thickness were baked for 30 minutes at 150 C. to give flexible,infusible products which showed no deterioration on subjecting toboiling water for 2 hours or to 5% aqueous NaOH at room temperature for2 hours.

A similar mixture of 69 parts of the dimer ester, 26 parts of the samepolyallyl glycidyl ether, and 0.12 part DMP-30 was found to give filmswhich converted to infusibility on baking for 30 minutes at 150 C. vAmixture of 69 parts of the dimer ester, 100 parts of Epon 1001, and 1.69parts of DMP-30 dissolved in methyl isobutyl ketone to give anonvolatile content of 60% had an initial viscosity of 2 poises,'aviscosity of 4.4 poises after 1 week, a viscosity of 36 poises after 40days, and a viscosity of 162 poises after 60 days.

EXAMPLE XXXIII A mixture of 70 parts of the trimer acid ester of ExampleXVII, 26.6 parts of the polyallyl glycidyl ether used in Example XXXII,and 0.97 part of DMP-30 dissolved in methyl isobutyl ketone to give anonvolatile EXAMPLE XXXIV A mixture of 60 parts (based on nonvolatile)of the cottonseed oil pitch ester of Example XVIII, 12 parts ofdiglycidyl ether of bisphenol A having an epoxide equivalent weight of190, and 1.4 parts of DMP-30 diluted to a 50% nonvolatile content withxylene was spread in a 16 0.003-inch wet film and baked for 18 minutesat 150 C. to give good conversion to an infusible film. The film wasvery flexible. EXAMPLE XXXV A mixture of 22 parts of the 50% solution ofthe trimer ester of Example XIX, 8 parts of a 50% solution of adiglycidyl ether of bisphenol A (epoxide equivalent weight of 190) inmethyl isobutyl ketone and 0.3 part of benzyl dimethyl amine was spreadin a 0.003-inch wet film and baked for 30 minutes at C. to give aninfusible, flexible film. When exposed to boiling water or to 5% aqueousNaOH at room temperature for 5 hours, this film exhibited no signs ofdeterioration.

EXAMPLE XXXVI A mixture of 20 parts of the 50% solution of the dimerester of Example XX, 2.6 parts of the polyallyl glycidyl ether used inExample XXXII and 0.12 part of DMP-30 was spread in a 0.003-inch wetfilm and baked for 30 minutes at C. to produce a very flexible,infusible product. This film showed no deterioration on exposure toboiling water for 5.5 hours and to 5% aqueous NaOH at 90 C. for 1 hour.

EXAMPLE )QQCVII A mixture of 10 parts of the 50% solution of the C acidester of Example XXI, 10 parts of a 50% solution of bisphenolA-epichlorohydrin epoxide resin having an epoxide equivalent weight of500, and 0.1 part DMP-30 was spread in a 0.003-inch wet film and heated30 minutes at 150 C. to give a very flexible, infusible film. This filmshowed no deterioration on exposure to boiling water for 5 .5 hours, orto 5% aqueous NaOH at room temperature for 3 hours.

It will be appreciated that while there are above disclosed but alimited number of embodiments of the product and process of theinvention herein presented, it is possible to produce still otherembodiments without departing from the inventive concept hereindisclosed, and it is to be understood that the invention is to belimited only by the scope of the appended claims.

What is claimed is:

1. A substantially gel-free, resinous polyhydric phenol having at least4 phenolic hydroxyls per molecule and having the formula X X lat-1 l lwhere A is the organic radical of an esterified alcohol which, prior toesterification, contains 1-3 alcoholic hydroxyl groups, X is a phenolicether radical and R is a polycarboxylic acid radical connected to Athrough an ester linkage.

2. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein XAX is a radical, which prior to esterification, is thereaction product of an excess of a dihydric phenol with an alcoholichydroxyl-containtaining dihalohydrin.

3. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein XAX is a radical, which prior fo'esterification, is thereaction product of an excess ofa'dihydric phenol with an epihalohydrin.

4. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein XAX is a radical, which prior to esterification, is thereaction product of an excess of a dihydric phenol with a diepoxide.

5. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein XAX is a radical, which prior to esterification, is thereaction product of an excess of his (4-hydroxy-phenyl) dimethyl methaneand epichlorohydrin.

6. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein XAX is a radical, which prior to esterification, is thereaction product of an 17 excess of tetrachloro bis (4hydroxy phenyl)dimethyl methane with 1,3-glycerol dichlorohydrin.

7. A substantially gel-free, resinous polyhdric phenol according toclaim 1 wherein XAX is a radical, which prior to esterification, is thereaction product of an excess of the methyl ester of 4-4-bis(4-hydroxyphenyl) pentanoic acid with diepoxybutane.

8. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, is anaromatic polycarboxylic acid.

9. A substantially gel-free, resinous polyhydric phenol according claim1 wherein R is a radical, which prior to esterification, is phthalicacid.

10. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, is analiphatic polycarboxylic acid.

11. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, is maleicacid.

12. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, issuccinic acid.

13. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, issebacic acid.

14. A substantially gel-free resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, is a longchain aliphatic acid in which the acid structure contains an aliphaticchain of at least 16 carbon atoms.

15. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, is apolymerized vegetable oil acid.

16. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, isdimerized 9-octadecenoic acid.

17. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, is apolycarboxylic acid having the structural formula (CH CH= CHCH (CH COzH)2 wherein n is an integer from 3 to 5.

18. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein R is a radical, which prior to esterification, is8,12-eicosandienedioic acid.

19. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein X-AX is a radical, which prior to esterification, is thereaction product of an excess of bis (4-hydroXy-phenyl) dimethyl methanewith epichlorohydrin and R is the residue of phthalic acid.

20. A substantially gel-free, resinous polyhydric phenol according toclaim 1 wherein X-AX is a radical, which prior to esterification, is thereaction product of an excess of his (4-hydroXy-phenyl) dimethyl methanewith epichlorohydrin and R is the residue of dimerized 9-octadecenoicacid.

References Cited in the file of this patent UNITED STATES PATENTS2,060,715 Arvin Nov. 10, 1936 2,503,726 Greenlee Apr. 11, 1950 2,592,560Greenlee Apr. 15, 1952

1. A SUBSTANTIALLY GEL-FREE, RESINOUS POLYHYDRIC PHENOL HAVING AT LEAST4 PHENOLIC HYDROXYLS PER MOLECULE AND HAVING THE FORMULA